2, 4, 5, 7, 8-pentavinyl-1, 3, 6-trioxacyclooctane and process for its production



llite tates This invention relates to a new chemical compound 2,4,5,7,8-pentavinyl-1,3, 6-trioxacyclooctane which has the structural formula UHF-CH CH=CH2 The new compound can be prepared by the cyclic condensation of divinyl glycol, i.e. divinyl ethylene glycol OHFOH-CHCH-CH=CH2 OH OH The reaction is preferably carried out in the presence of a suitable catalyst, at a moderately elevated temperature, in the substantial absence of oxygen and in the presence of a vinyl polymerization inhibitor.

Examples of suitable catalysts are the cupric salts of common acids, for example cupric chloride, bromide, sulfate, nitrate and acetate. These can also be used in their hydrated forms and in the form of mixtures or solutions. A preferred catalyst is cupric chloride. The preferred proportions are in the general range of 0.1%- 10% by weight based on the amount of divinyl glycol used.

For the purpose of minimizing the reaction time, a moderately elevated temperature in the range of about 50-l50 C. is preferred. Higher temperatures which are below the decomposition temperature of the components of the reaction mixture can also be used but tend to increase undesirable side reactions and to cause the desired product to polymerize.

lAlthough absolute exclusion of oxygen from the reaction mixture is not necessary, the reaction is preferably carried out in a low oxygen environment, for example in a vented but otherwise closed vessel continuously swept with an inert gas such as nitrogen.

Since both the starting material, divinyl glycol, and the new compound are unsaturated and susceptible to polymerization, a vinyl polymerization inhibitor is preferably present during the reaction. However such an inhibitor is not necessary, particularly a low reaction temperature and rigorous exclusion of oxygen are practiced in the process. Suitable inhibitors are those well known in the vinyl polymerization art, for example phenothiazine, hydroquinone, ditertiarybutyl hydroquinone, pyrocatechol and par-ahydroxydiphenyl amine. The preferred proportions are in the general range of O.1%2% by weight based on the amount of diviuyl glycol. In most uses of the new compound, the inhibitor is removed or at least reduced to an innocuous concentration.

The new compound is useful as a monomer or co- 3,090,7d0 Patented May 21, 1963 monomer in the preparation of homopolymers and also copolyrners with other compounds containing the CH C group :by conventional vinyl polymerization techniques. Because of its high degree of vinyl unsaturation or so-called polyfunctionality, it is useful as a cross linking agent for polymers from unsaturated monomers.

The new compound is also useful, in both clear and pigmented coating compositions, as an air-drying filmforming material. Air-drying is the property of spontaneously converting upon prolonged exposure to air (oxygen) into a coating which is insoluble in or only somewhat softened by a solvent (e.g. paint thinner) in which the starting material dissolves. 'As an analogy, paints and varnishes comprise an air-drying film-forming substance, e.g. linseed oil or the like. Paint drier is usually incorporated in air-drying coating compositions to speed the drying process. In this invention, cobalt-based driers (eg. cobalt napthenate, linoleate, :oleate, octoate, resinate, tallate, linoresinate, nitrate, sulfate) are preferred. Cobaltous salts of half esters of dicarboxylic acids are especially preferred driers because they are most effective in yielding fast drying. A particularly preferred drier is cobaltous butyl phthalate because of its easy solubility in the new compound. Conventional paint driers such as the soaps and salts of lead, manganese, iron or other siccative metals can also be used in proportions up to 2%-3% of metal, but preferably in addition to a cobalt drier. The preferred proportion of cobalt drier is in the general range of 0.01%-1% by weight of cobalt in the drier com-pound based on the Weight of the new compound of this invention.

The following examples are illustrative.

Example 1 A mixture of 114 grams of divinyl glycol, 5 grams of cupric chloride dihydrate catalyst (3.94 grams CuCI and 0.5 gram of phenothiazine polymerization inhibitor was charged into a three-necked flask equipped with an agitator, thermometer, nitrogen inlet and still head with condenser. Air '(oxygen) was displaced by nitrogen, and a stream of nitrogen was continued throughout the reaction period. flhe reaction mixture was heated at approximately C. for about six hours with constant moderate agitation. During this period 8.5 ml. of water and 0.7 ml. of a light yellow oil were distilled oif.

The reaction mixture was cooled to approximately room temperature and was then washed with 200 ml. of water. Upon settling, the water-insoluble layer was separated and was dried over magnesium sulfate. Following filtration, the remaining liquid was fractionally distilled under vacuum in a three foo-t spinning band column. The fraction which distilled at 49 C. and 0.22 mm. Hg was retained and was subsequently determined by chemical and infrared analysis to be the compound of this invention, namely 2,4,5,7,8-pentavinyl1,3,6-trioxacyclooctane, a colorless odorless liquid.

Example 2 In 10 grams of the compound of Example 1 was admixed 0.5 ml. of cobaltous butyl phthalate drier solution in toluene (10 mg. of Co per ml. of solution). A coating of the resulting liquid mixture was drawn :on a clean steel panel under a doctor knife having a clearance of about 3 mils. The wet coated panel was permitted to dry by ex- 3 4 posure to air at room temperature (about 25 C.). In 2. The process of preparing 2,4,5,7,8-pentaviny-l-l,3,6- about 4 hours the coating was dry, cl a ard a d :trioxacyclooct'ane which process consists essentially of adherent. heating divinyl glycol at a temperature of about 50- 11 10 B111 Coating 51111113113 Prepared dned 5 6 150 C. in the presence of acupric sal t as acatalys-t.

ours. 5

In this and in other coating compositions of this in- References Cited in the file of this patent vention, lower temperatures and/'or lower concentrations of drier generally increase the drying time. Artificially UNITED STATES PATENTS elevated temperatures, e.g. 50100 C., a d/01' hig r 2,293,868 Toussaint Aug. 25, 1942 concentrations of drier in the renge set for h h r inbefor 10 2,623,833 Hochstadt 30, 195

Y decfeass the drying llme- 2,733,237 Zweig Apr, 9, 1957 7 1mm: 2,876,127 Ware Mar. 3, 1959 1. 2,4,5,7,S-pentavinyld,3,6-trioxacyclooctane. 

1. 2,4,5,7,8-PENTAVINYL-1,3,6-TRIOXACYCLOOCTANE. 